CN101305042B - 经填充的聚合物复合材料 - Google Patents
经填充的聚合物复合材料 Download PDFInfo
- Publication number
- CN101305042B CN101305042B CN2006800420092A CN200680042009A CN101305042B CN 101305042 B CN101305042 B CN 101305042B CN 2006800420092 A CN2006800420092 A CN 2006800420092A CN 200680042009 A CN200680042009 A CN 200680042009A CN 101305042 B CN101305042 B CN 101305042B
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- China
- Prior art keywords
- block
- gather
- vinylbenzene
- divinyl
- isoprene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Abstract
本发明公开了经填充的树脂复合材料，所述复合材料包含至少一种聚合物树脂和微球，其中所述微球具有25微米或更小的平均尺寸D50和至少10,000PSI(68.8Mpa)的10％抗挤强度。这类述树脂呈现令人惊奇且以前未曾获得的卓越物理特性的组合。本发明还公开了由上述复合材料制得的制品。
Description
技术领域
本发明涉及填充有中空微球或泡沫的聚合物或树脂复合材料。
背景技术
在本领域中已知，将中空微球掺入到聚合物复合材料中，如热固性和热塑性树脂，来替代昂贵的聚合物组分或降低所得制品的密度。例如，3M Company销售3M牌S60HS玻璃泡，该玻璃泡尤其可用作聚合物复合材料中的填料。上述玻璃泡具有29微米的平均尺寸D50和45微米的平均尺寸D90。
虽然玻璃泡通常可成功地用于降低最终复合材料的密度，但是上述所得复合材料通常呈现不期望的某些物理特性损耗，如冲击强度和拉伸强度。向聚合物基质中掺入非补强填料可致使经填充聚合物混料的机械强度(张力、冲击等)降低。非补强填料可被定义为纵横比(长度/直径)小于2的任何颗粒。据信，机械强度的损耗主要是由于填料导致聚合物链缠结能力被破坏，并且还应归因于聚合物与填料间的低效粘合；其中假定粘合强度小于聚合物链自身的拉伸强度。已知使用偶联剂(例如硅烷处理物)来改善填料颗粒与聚合物基质间的粘结强度，但是期望所得复合材料物理特性有进一步的改善。
经填充的树脂复合材料的示例性实例公开于美国专利No.3,769,126(Kolek)、4,243,575(Myers等人)、4,923,520(Anzai等人)、和5,695,851(Watanabe等人)以及EP专利申请No.1,142,685(Akesson)中。
需要经改善的填充有中空微球的聚合物或树脂基质复合材料。
发明内容
本发明涉及含有中空微球或泡沫的聚合物或树脂复合材料以及由上述复合材料制得的制品。已发现，使用如下所述的某些中空微球可制得呈现改善特性的所得复合材料。
简而言之，本发明的复合材料包含聚合物或树脂基质和多个如本文所述的中空微球。本发明的复合材料不同于传统的复合材料，因为所述微球比用于先前已知复合材料中的微球更小且更坚固。
本发明的复合材料呈现令人惊奇且以前未曾获得的卓越物理特性的组合，包括冲击强度和伸长性。根据本发明，由上述复合材料制得的制品可提供令人惊奇的有利结果。
具体实施方式
为了本发明的目的，此专利申请中使用的以下术语定义如下：
“平均尺寸D50”是平均50％(按数目计)的微球直径等于或大于其值的直径。
“平均尺寸D90”是平均90％(按数目计)的微球直径等于或大于其值的直径。
本发明的复合材料包含聚合物或树脂基质和多个中空微球。在某些情况下，本发明的复合材料基本上由上述基质、如下文所述的微球所需的添加剂构成。
微球
用于本发明复合材料中的中空微球将通常具有25微米或更小的平均尺寸D50，以及至少10,000PSI(68.8Mpa)的10％抗挤强度，所述抗挤强度可采用ASTM D3102-72；“Hydrostatic Collapse Strengthof Hollow Glass Microspheres”来测定。
泡沫的10％抗挤强度优选为至少15,000PSI(103Mpa)，更优选至少18,000PSI(124Mpa)，以抵御在由上述复合材料制备复合材料制品时通常遇到的热塑性挤出和注塑成形操作。
用于本发明复合材料中的泡沫小于传统上用于复合材料中的那些。通常，所述泡沫将具有约25微米或更小，优选约20微米或更小的平均尺寸D50。通常，所述泡沫将具有约50微米或更小，优选约40微米或更小的平均尺寸D90。在一些示例性的优选实施例中，所述泡沫具有约25微米或更小的平均D50尺寸和约50微米或更小的平均D90尺寸，并且在其它一些示例性的优选实施例中，甚至具有约20微米或更小的平均D50尺寸和约40微米或更小的平均D90尺寸。
所述微球优选包括玻璃或陶瓷材料，最优选为中空玻璃微球。
聚合物基质
所述聚合物基质通常为任何其中可使用中空微球的热塑性或热固性聚合物或共聚物。所述聚合物基质包括烃类和非烃类聚合物。可用的聚合物基质的实例包括但不限于：聚酰胺、聚酰亚胺、聚醚、聚氨酯、聚烯烃、聚苯乙烯、聚酯、聚碳酸酯、聚酮、聚脲、聚乙烯树脂、聚丙烯酸酯、聚甲基丙烯酸酯、以及氟化的聚合物。
一种优选的应用涉及可熔融加工的聚合物，其中在形成挤出或模制聚合物制品之前，在熔融混合阶段分散所述组分。
为了本发明的目的，可熔融加工的组合物是能够被加工、同时所述组合物的至少一部分为熔融状态的那些。
传统上公认的熔融加工方法和设备可用于加工本发明的组合物。熔融加工实践的非限制性实例包括挤出、注塑成形、间歇混合、旋转模制和拉挤。
优选的聚合物基质包括：聚烯烃(如高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、直链低密度聚乙烯(LLDPE)、聚丙烯(PP))、聚烯烃共聚物(如乙烯-丁烯、乙烯-辛烯、乙烯一乙烯醇)、聚苯乙烯、聚苯乙烯共聚物(如高抗冲聚苯乙烯、丙烯腈丁二烯苯乙烯共聚物)、聚丙烯酸酯、聚甲基丙烯酸酯、聚酯、聚氯乙烯(PVC)、含氟聚合物、液晶聚合物、聚酰胺、聚醚酰亚胺、聚苯硫醚、聚砜、聚缩醛树脂、聚碳酸酯、聚苯醚、聚氨酯、热塑性弹性体、环氧树脂、醇酸、三聚氰胺、酚类、脲、乙烯酯，或它们的组合。
弹性体是适用作聚合物基质的另一亚类聚合物。可用的弹性体聚合物树脂(即弹性体)包括热塑性和热固性弹性体聚合物树脂，例如聚丁二烯、聚异丁烯、乙烯-丙烯共聚物、乙烯-丙烯-双烯三元共聚物、磺化的乙烯-丙烯-双烯三元共聚物、聚氯丁二烯、聚(2，3-二甲基丁二烯)、聚(丁二烯-共-戊二烯)、氯磺化聚乙烯、聚硫化物弹性体、硅氧烷弹性体、聚(丁二烯-共-腈)、氢化腈-丁二烯共聚物、丙烯酸弹性体、乙烯-丙烯酸酯共聚物。
可用的热塑性弹性体聚合物树脂包括由玻璃状嵌段或晶状嵌段构成的嵌段共聚物，所述嵌段如聚苯乙烯、聚(乙烯基甲苯)、聚(叔丁基苯乙烯)、和聚酯，而所述弹性体嵌段如聚丁二烯、聚异戊二烯、乙烯-丙烯共聚物、乙烯-丁烯共聚物、聚醚酯等，如由Shell ChemicalCompany(Houston，Texas)以商品名“KRATON”市售的聚(苯乙烯-丁二烯-苯乙烯)嵌段共聚物。还可使用这些上述弹性体聚合物树脂的共聚物和/或混合物。
可用的聚合物基质还包括氟聚合物，即至少部分氟化的聚合物。可用的氟聚合物包括例如可由单体制得的那些(例如，通过自由基聚合反应)，所述单体包括：25三氟氯乙烯、2-氯五氟丙烯、3-氯五氟丙烯、偏二氟乙烯、三氟乙烯、四氟乙烯、1-氢五氟丙烯、2-氢五氟丙烯、1，1-二氯氟乙烯、二氯二氟乙烯、六氟丙烯、氟乙烯、全氟化乙烯基醚(例如全氟代(烷氧基乙烯基醚)，如CF3OCF2CF2CF2OCF＝CF2，或全氟代(烷基乙烯基醚)，如全氟代(甲基乙烯基醚)或全氟代(丙基乙烯基醚))、固化点单体如含腈单体(例如CF2＝CFO(CF2)LCN、CF2＝CFO[CF2CF(CF3)O]q(CF2O)yCF(CF3)CN、CF2＝CF[OCF2CF(CF3)]rO(CF2)tCN或CF2＝CFO(CF2)uOCF(CF3)CN，其中L为2至12；q为0至4；r为1至2；y为0至6；t为1至4；并且u为2至6)、含溴单体(例如Z-Rf-Ox-CF＝CF2，其中Z为Br或I，Rf为取代或未取代的C1-C12含氟亚烷基，其可以是全氟化的，并且可含有一个或多个醚氧原子，并且x未0或1)；或它们的组合，可选与其它非氟化单体如乙烯或丙烯组合。上述氟聚合物的具体实例包括：聚偏氟乙烯；四氟乙烯、六氟丙烯和偏二氟乙烯的共聚物；四氟乙烯、六氟丙烯、全氟丙基乙烯基醚和偏二氟乙烯的共聚物；四氟乙烯-六氟丙烯共聚物；四氟乙烯-全氟代(烷基乙烯基醚)共聚物(如四氟乙烯全氟(丙基乙烯基醚))；以及它们的组合。
可用的市售热塑性含氟聚合物包括例如以商品名DYNEONTMTHV(例如“THV 220”、“THV 400G”、“THV 500G”、“THV 815”和“THV 610X”)、“PVDF”、“PVF”、“TFEP”、“PFA”、“HTE”、“ETFE”和“FEP”售自Dyneon，LLC，Oakdale，Minnesota的那些；以商品名“KYNAR”(例如“KYNARTM 740”)售自AtofinaChemicals，Philadelphia，Pennsylvania的那些；以商品名“HYLAR”(例如“HYLARTM 700”)和“HALARTM ECTFE”售自Solvay Solexis，Thorofare，New Jersey的那些；Allied Signal PCTFE；和DuPontTEFLONTM。
本发明复合材料中的聚合物树脂组分可包含嵌段共聚物，如2004年11月16日提交的受让人的共同未决的美国临时专利申请号60/628335(Docket No.60207US002)中所述。
所述嵌段共聚物经由官能团部分与微球相互作用。官能团嵌通常具有一个或多个极性部分，例如，酸(如-CO2H、-SO3H、-PO3H)；-OH；-SH；伯胺、仲胺或叔胺；铵N-取代或未取代的酰胺和内酰胺；N-取代或未取代的硫代酰胺和硫代内酰胺；酸酐；直链或环状醚和聚醚；异氰酸酯；氰酸酯；腈；氨基甲酸酯；脲；硫脲；杂环胺(例如吡啶或咪唑)。用于引入上述基团的可用单体包括例如酸(例如丙烯酸、甲基丙烯酸、衣康酸、马来酸、富马酸，并且包括经由异丁烯酸叔丁酯单体单元酸催化去保护反应生成的甲基丙烯酸官能团，如美国专利公布No.2004/0024130(Nelson等人)中所述)；丙烯酸酯和甲基丙烯酸酯(例如丙烯酸2-羟基乙酯)、丙烯酰胺和甲基丙烯酰胺、N-取代的和N，N-二取代的丙烯酰胺(例如N-叔丁基丙烯酰胺、N，N-(二甲氨基)乙基丙烯酰胺、N，N-二甲基丙烯酰胺、N，N-二甲基甲基丙烯酰胺)、N-乙基丙烯酰胺、N-羟乙基丙烯酰胺、N-辛基丙烯酰胺、N-叔丁基丙烯酰胺、N，N-二甲基丙烯酰胺、N，N-二乙基丙烯酰胺、和N-乙基-N-二羟基乙基丙烯酰胺)、脂族胺(例如3-二甲基氨基丙胺、N，N-二甲基乙二胺)；和杂环单体(例如2-乙烯基吡啶、4-乙烯基吡啶、2-(2-氨乙基)吡啶、1-(2-氨乙基)吡咯烷、3-氨基奎宁啶、N-乙烯基吡咯烷酮和N-乙烯基己内酰胺)。
其它适宜的嵌段通常具有一个或多个疏水部分，例如脂肪族和芳族烃部分，诸如具有至少约4、8、12或甚至18个碳原子的那些；氟化脂肪族烃和/或氟化芳族烃部分，例如具有至少约4、8、12或甚至18个碳原子的那些；以及硅氧烷部分。
可用于引入上述嵌段的单体的非限制性实例包括：烃类烯烃诸如乙烯、丙烯、异戊二烯、苯乙烯和丁二烯；环状硅氧烷，诸如十甲基环五硅氧烷和十甲基四硅氧烷；氟化烯烃，诸如四氟乙烯、六氟丙烯、三氟乙烯、二氟乙烯和氟氯乙烯；非氟化丙烯酸烷基酯和甲基丙烯酸烷基酯，诸如丙烯酸丁酯、甲基丙烯酸异辛酯、丙烯酸盐月桂酯、丙烯酸硬脂基酯；氟化丙烯酸酯，诸如具有化学式H2C＝C(R2)C(O)O-X-N(R)SO2Rf′结构的全氟代烷基磺酰胺烷基丙烯酸酯和甲基丙烯酸酯，其中：Rf′为-C6F13、-C4F9、或-C3F7；R为氢、C1至C10烷基、或C6-C10芳基；并且X为二价连接基团。优选的实例包括C4F9SO2N(CH3)C2H4OC(O)NH(C6H4)CH2C6H4NHC(O)OC2H4OC(O)CH＝CH2或
上述单体易于由市售源或根据例如美国专利公布No.2004/0023016(Cernohous等人)中步骤制备而得，其公开内容以引用的方式并入本文。
具有官能团部分的可用嵌段共聚物的其它非限制性实例包括：聚(异戊二烯-嵌段-4-乙烯基吡啶乙烯基吡啶)；聚(异戊二烯-嵌段-甲基丙烯酸)；聚(异戊二烯-嵌段-N，N-(二甲基氨基)丙烯酸乙酯)；聚(异戊二烯-嵌段-2-二乙基氨基苯乙烯)；聚(异戊二烯-嵌段-甲基丙烯酸缩水甘油酯)；聚(异戊二烯-嵌段-甲基丙烯酸2-羟乙酯)；聚(异戊二烯-嵌段-N-乙烯基吡咯烷酮)；聚(异戊二烯-嵌段-甲基丙烯酸酐)；聚(异戊二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸))；聚(苯乙烯-嵌段-4-乙烯基吡啶)；聚(苯乙烯-嵌段-2-乙烯基吡啶)；聚(苯乙烯-嵌段-丙烯酸)；聚(苯乙烯-嵌段-甲基丙烯酰胺)；聚(苯乙烯-嵌段-N-(3-氨丙基)甲基丙烯酰胺)；聚(苯乙烯-嵌段-N，N-(二甲基氨基)丙烯酸乙酯)；聚(苯乙烯-嵌段-2-二乙基氨基苯乙烯)；聚(苯乙烯-嵌段-甲基丙烯酸缩水甘油酯)；聚(苯乙烯-嵌段-甲基丙烯酸2-羟乙酯)；聚(苯乙烯-嵌段-N-乙烯基吡咯烷酮共聚物)；聚(苯乙烯-嵌段-异戊二烯-嵌段-4-乙烯基吡啶)；聚(苯乙烯-嵌段-异戊二烯-嵌段-甲基丙烯酸缩水甘油酯)；聚(苯乙烯-嵌段-异戊二烯-嵌段-甲基丙烯酸)；聚(苯乙烯-嵌段-异戊二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸))；聚(苯乙烯-嵌段-异戊二烯-嵌段-甲基丙烯酸酐)；聚(丁二烯-嵌段-4-乙烯基吡啶)；聚(丁二烯-嵌段-甲基丙烯酸)；聚(丁二烯-嵌段-N，N-(二甲基氨基)丙烯酸乙酯)；聚(丁二烯-嵌段-2-二乙基氨基苯乙烯)；聚(丁二烯-嵌段-甲基丙烯酸缩水甘油酯)；聚(丁二烯-嵌段-甲基丙烯酸2-羟乙酯)；聚(丁二烯-嵌段-N-乙烯基吡咯烷酮)；聚(丁二烯-嵌段-甲基丙烯酸酐)；聚(丁二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸)；聚(苯乙烯-嵌段-丁二烯-嵌段-4-乙烯基吡啶)；聚(苯乙烯-嵌段-丁二烯-嵌段-甲基丙烯酸)；聚(苯乙烯-嵌段-丁二烯-嵌段-N，N-(二甲基氨基)丙烯酸乙酯)；聚(苯乙烯-嵌段-丁二烯-嵌段-2-二乙基氨基苯乙烯)；聚(苯乙烯-嵌段-丁二烯-嵌段-甲基丙烯酸缩水甘油酯)；聚(苯乙烯-嵌段-丁二烯-嵌段-甲基丙烯酸2-羟乙酯)；聚(苯乙烯-嵌段-丁二烯-嵌段-N-乙烯基吡咯烷酮)；聚(苯乙烯-嵌段-丁二烯-嵌段-甲基丙烯酸酐)；聚(苯乙烯-嵌段-丁二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸))；以及氢化形式的聚(丁二烯-嵌段-4-乙烯基吡啶)、聚(丁二烯-嵌段-甲基丙烯酸)、聚(丁二烯-嵌段-N，N-(二甲基氨基)丙烯酸乙酯)、聚(丁二烯-嵌段-2-二乙基氨基苯乙烯)、聚(丁二烯-嵌段-甲基丙烯酸缩水甘油酯)、聚(丁二烯-嵌段-甲基丙烯酸2-羟乙酯)、聚(丁二烯-嵌段-N-乙烯基吡咯烷酮)、聚(丁二烯-嵌段-甲基丙烯酸酐)、聚(丁二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸))、聚(异戊二烯-嵌段-4-乙烯基吡啶)、聚(异戊二烯-嵌段-甲基丙烯酸)、聚(异戊二烯-嵌段-N，N-(二甲基氨基)丙烯酸乙酯)、聚(异戊二烯-嵌段-2-二乙基氨基苯乙烯)、聚(异戊二烯-嵌段-甲基丙烯酸缩水甘油酯)、聚(异戊二烯-嵌段-甲基丙烯酸2-羟乙酯)、聚(异戊二烯-嵌段-N-乙烯基吡咯烷酮)、聚(异戊二烯-嵌段-甲基丙烯酸酐)、聚(异戊二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸))、聚(苯乙烯-嵌段-异戊二烯-嵌段-甲基丙烯酸缩水甘油酯)、聚(苯乙烯-嵌段-异戊二烯-嵌段-甲基丙烯酸)、聚(苯乙烯-嵌段-异戊二烯-嵌段-甲基丙烯酸酐-共-甲基丙烯酸)、苯乙烯-嵌段-异戊二烯-嵌段-甲基丙烯酸酐、聚(苯乙烯-嵌段-丁二烯-嵌段-4-乙烯基吡啶)、聚(苯乙烯-嵌段-丁二烯-嵌段-甲基丙烯酸)、聚(苯乙烯-嵌段-丁二烯-嵌段-N，N-(二甲基氨基)丙烯酸乙酯)、聚(苯乙烯-嵌段-丁二烯-嵌段-2-二乙基氨基苯乙烯)、聚(苯乙烯-嵌段-丁二烯-嵌段-甲基丙烯酸缩水甘油酯)、聚(苯乙烯-嵌段-丁二烯-嵌段-甲基丙烯酸2-羟乙酯)、聚(苯乙烯-嵌段-丁二烯-嵌段-N-乙烯基吡咯烷酮)、聚(苯乙烯-嵌段-丁二烯-嵌段-甲基丙烯酸酐)、聚(苯乙烯-嵌段-丁二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸)、聚(MeFBSEMA-嵌段-甲基丙烯酸)(其中“MeFBSEMA”是指2-(N-甲基全氟代丁基磺酰胺基)甲基丙烯酸乙酯，如可得自3M Company，Saint Paul，Minnesota)、聚(MeFBSEMA-嵌段-甲基丙烯酸叔丁酯)、聚(苯乙烯-嵌段-甲基丙烯酸叔丁酯-嵌段-MeFBSEMA)、聚(苯乙烯-嵌段-甲基丙烯酸酐-嵌段-MeFBSEMA)、聚(苯乙烯-嵌段-甲基丙烯酸-嵌段-MeFBSEMA)、聚(苯乙烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸)-嵌段-MeFBSEMA))、聚(苯乙烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸-共-MeFBSEMA))、聚(苯乙烯-嵌段-(甲基丙烯酸叔丁酯-共-MeFBSEMA))、聚(苯乙烯-嵌段-异戊二烯-嵌段-甲基丙烯酸叔丁酯-嵌段-MeFBSEMA)、聚(苯乙烯-异戊二烯-嵌段-甲基丙烯酸酐-嵌段-MeFBSEMA)、聚(苯乙烯-异戊二烯-嵌段-甲基丙烯酸-嵌段-MeFBSEMA)、聚(苯乙烯-嵌段-异戊二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸)-嵌段-MeFBSEMA)、聚(苯乙烯-嵌段-异戊二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸-共-MeFBSEMA))、聚(苯乙烯-嵌段-异戊二烯-嵌段-(甲基丙烯酸叔丁酯-共-MeFBSEMA))、聚(MeFBSEMA-嵌段-甲基丙烯酸酐)、聚(MeFBSEMA-嵌段-(甲基丙烯酸-共-甲基丙烯酸酐))、聚(苯乙烯-嵌段-(甲基丙烯酸叔丁酯-共-MeFBSEMA))、聚(苯乙烯-嵌段-丁二烯-嵌段-甲基丙烯酸叔丁酯-嵌段-MeFBSEMA)、聚(苯乙烯-丁二烯-嵌段-甲基丙烯酸酐-嵌段-MeFBSEMA)、聚(苯乙烯-丁二烯-嵌段-甲基丙烯酸-嵌段-MeFBSEMA)、聚(苯乙烯-嵌段-丁二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸)-嵌段-MeFBSEMA)、聚(苯乙烯-嵌段-丁二烯-嵌段-(甲基丙烯酸酐-共-甲基丙烯酸-共-MeFBSEMA))、和聚(苯乙烯-嵌段-丁二烯-嵌段-(甲基丙烯酸叔丁酯-共-MeFBSEMA))。
一般来讲，应选择嵌段共聚物以使得至少一个嵌段能够与微球互相作用。嵌段共聚物中剩余嵌段的选择通常由嵌段共聚物将结合的任何聚合物树脂的性质来决定。
所述嵌段共聚物可以是末端官能化的聚合材料，其可通过使用官能团引发剂或通过封端活性聚合物链来合成，如本领域中传统上所认识的那样。本发明末端官能化的聚合材料可包含在至少一个链末端具有官能团封端的聚合物。所述聚合物可以是均聚物、共聚物或嵌段共聚物。对那些具有多个链末端的聚合物而言，所述官能团可相同或不同。官能团的非限制性实例包括胺、酸酐、醇、羧酸、硫醇、马来酸酯、硅烷和卤化物。可采用使用本领域已知活性聚合方法的末端官能化策略来提供这些材料。
可使用任何量的嵌段共聚物，然而通常所述嵌段共聚物的含量按重量计在最多5％的范围内。
偶联剂
在一个优选的实施例中，可用偶联剂来处理微球以增强微球与聚合物树脂间的交互作用。希望选择一种偶联剂，其可匹配或提供与所选聚合物制剂中相应官能团的适宜反应性。偶联剂的示例性实例包括锆酸盐、硅烷或钛酸盐。代表性的钛酸盐和锆酸盐偶联剂是本领域内的技术人员已知的，并且对这些材料的使用和选择标准详细总结可见于Monte，S.J.(Kenrich Petrochemicals，Inc.)的“
ReferenceManual-Titanate，Zirconate and Aluminate Coupling Agents”第三修订版(1995年3月)中。如果使用偶联剂，则一般其含量按重量计为约1％至3％。
适宜的硅烷可通过缩合反应以与硅质填料形成硅氧烷链接，而连接到玻璃表面上。这种处理可使填料更可润湿，或促进材料对微球表面的粘合。这提供了致使无机填料与有机基质间共价、离子或偶极连接的机制。根据所期望的具体官能团来选择硅烷偶联剂。例如，氨基硅烷玻璃处理物适用于连接含有酸酐、环氧树脂或异氰酸酯基团的嵌段共聚物。作为另外一种选择，具有酸性官能团的硅烷处理物需要选择嵌段共聚物，以具有能够进行基于酸的交互作用、能够进行离子或氢键合行为的嵌段。另一个实现玻璃微球-嵌段共聚物紧密交互作用的方法是用含有可聚合部分的适宜偶联剂使微球表面官能化，从而将所述材料直接引入到聚合物主链中。可聚合部分的实例是含有烯属官能团诸如苯乙烯、丙烯酸和甲基丙烯酸部分的材料。适宜的硅烷偶合策略概述于Barry Arkles的“Silane Coupling Agents：Connecting AcrossBoundaries”第165-189页(Gelest Catalog 3000-A Silanes andSilicones：Gelest Inc.Morrisville，PA)中。
其它示例性的偶联剂实例包括马来酸酐改性的聚丙烯和聚乙烯。
适宜偶联剂的选择将部分取决于树脂和微球的构成，并且易于由本领域普通技术人员实施。
其它添加剂
如果需要，本发明的复合材料还可包含其它所需添加剂和试剂。示例性的实例包括：颜料、增粘剂、阻燃剂、UV吸收剂、抗光剂、抗粘连剂、增塑剂、韧化剂、抗冲改性剂、抗氧化剂、成核剂、分散剂、抗微生物剂、抗静电剂和加工助剂。
制品
本发明的复合材料可用于制备多种所需制品。示例性实例包括运输应用，诸如仪器芯板、发动机罩、侧面抗冲板、缓冲器、汽车仪表板、O形环、垫圈、制动块和软管；模制家用部件；复合材料薄片；热成形结构组件；以及线材和缆材覆层。其它示例性实例包括灌注化合物、壁板、结构性复合材料树脂、塑性容器和货盘。
通过以下示例性实例来进一步说明本发明。
实例
| 指示词 | 化学式、结构和/或名称 | 可获得性 |
| Nylon 6，6 | ZYTELTM 101L：熔融指数为60g/10m275℃，Tg为50℃，Tm为260-262℃，并且密度为1.14g/cm3 | DuPont，Wilmington，DE |
| S60HS | 玻璃泡；S60HS，密度为0.6g/cm3，18,000psi(124.0Mpa)10％抗挤强度 | 3M Company，St.Paul，MN |
复合材料的混合和模制
所有样本均在Berstorff Ultra Glide双螺杆挤出机(TSE；25mm螺旋直径；长度与直径的比率为36∶1；得自BerstorffGmbH，Hannover，Germany)中混合，所述挤出机配备有用于微球和玻璃纤维的顶部进料器、水浴和造球机附件。螺旋速度在140至160rpm范围内。温度设定值在200°F至575°F(93℃至302℃)范围内，而实际值在500°F至575°F(93℃至260℃)范围内。TSE通过量为约10lbs/hr。
然后在150ton Engel注塑成形机(得自ENGEL GmbH，Schwertberg，Austria)上，使用ASTM四腔模具，模制测试样品。所用螺旋直径为30mm，并且注射压力保持低于18,000psi(124Mpa)，以最大程度地减少微球破损。
测试方法
使用以下测试方法。
依照ASTM D-256来测定缺口悬臂梁式冲击强度，而依照ASTM D-4812来测定无缺口悬臂梁式冲击强度。
依照ASTM测试方法D-638来测定抗拉模量，并且以Mpa为单位记录。
依照ASTM测试方法D-638来测定最终拉伸强度，并且以Mpa为单位记录。
依照ASTM测试方法D-790来测定挠性模量，并且以Mpa为单位记录。
依照ASTM测试方法D-790来测定最终挠性模量，并且以Mpa为单位记录。
依照ASTM测试方法D-638来测定断裂伸长率，并且以％来记录。
依照ASTM D-2840-69“Average True Particle Density ofMicrospheres”，使用以商品名“ACCUPYC 1330 PYCNOMETER”得自Micromeritics(Norcross，Georgia)的全自动化气体排量密度仪，来测定注塑成形复合材料的密度。
物理测定步骤
使用Micromeretics Accupyc 1330 Helium Pycnometer(得自Micromeritics Instrument Corporation，Norcross，GA)，测定注塑成形复合材料样本的密度。使用列于表1中的ATSTM标准测试方法，测定注塑成形复合材料的机械特性和热特性。
表1
| 测试 | 指示词 | ASTM# |
| 抗拉模量(Mpa) | TM | D-638 |
| 最终拉伸强度(Mpa) | TS | D-638 |
| 挠性模量(Mpa) | FM | D-790 |
| 最终挠性强度(Mpa) | FS | D-790 |
| 断裂伸长率(％) | EL | D-638 |
| 无缺口悬臂梁式冲击强度(J/cm) | UI | D-4812 |
| 缺口悬臂梁式冲击强度(J/cm) | NI | D-256 |
表2
表2：市售S60HS中空玻璃微球和实验微球A和B的密度、强度和尺寸
在双螺杆挤出机上，将S60HS微球和微球A和B混合到Nylon 6，6树脂中。然后对多种制剂进行ASTM测试样本注模，并且按照上文指定的ASTM测试，测定代表性的机械性能。机械性能测试结果示于表3中。
表3：制剂和所得机械性能的描述
结果显示，通过将更小、更强固的泡沫A或B掺入到Nylon 6，6中，可获得与将S60HS掺入到Nylon 6，6中相比改善的机械性能(冲击强度、拉伸强度、张力伸长和挠曲强度)。
本文引用了若干专利申请和专利；每一项专利申请或专利均全文以引用方式并入。
在不脱离本发明的范围和精神的前提下，本发明的各种修改和更改对于本领域技术人员将是显而易见的。
Claims (4)
1.一种经填充的树脂复合材料，其包含至少一种聚合物树脂和泡沫，其中所述泡沫选自由下列物质组成的组：玻璃泡和陶瓷泡，并且所述泡沫具有25微米或更小的平均尺寸D50，具有50微米或更小的平均尺寸D90和至少10,000PSI的10％抗挤强度。
2.根据权利要求1所述的复合材料，其中所述泡沫具有20微米或更小的平均尺寸D50。
3.根据权利要求1所述的复合材料，其中所述复合材料中75％以上的所述泡沫具有20微米或更小的平均尺寸D50和40微米或更小的平均尺寸D90。
4.一种制品，其包含根据权利要求1所述的复合材料。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/271,025 | 2005-11-10 | ||
| US11/271,025 US20070104943A1 (en) | 2005-11-10 | 2005-11-10 | Filled polymer composites |
| PCT/US2006/043205 WO2007058812A1 (en) | 2005-11-10 | 2006-11-07 | Filled polymer composites |
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| Publication Number | Publication Date |
|---|---|
| CN101305042A CN101305042A (zh) | 2008-11-12 |
| CN101305042B true CN101305042B (zh) | 2012-05-02 |
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| CN2006800420092A Expired - Fee Related CN101305042B (zh) | 2005-11-10 | 2006-11-07 | 经填充的聚合物复合材料 |
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| Country | Link |
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| US (1) | US20070104943A1 (zh) |
| EP (1) | EP1945709A4 (zh) |
| JP (1) | JP2009516023A (zh) |
| KR (1) | KR20080075105A (zh) |
| CN (1) | CN101305042B (zh) |
| BR (1) | BRPI0618474A2 (zh) |
| TW (1) | TWI441859B (zh) |
| WO (1) | WO2007058812A1 (zh) |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200730569A (en) | 2007-08-16 |
| EP1945709A4 (en) | 2015-03-18 |
| EP1945709A1 (en) | 2008-07-23 |
| TWI441859B (zh) | 2014-06-21 |
| US20070104943A1 (en) | 2007-05-10 |
| BRPI0618474A2 (pt) | 2011-08-30 |
| WO2007058812A1 (en) | 2007-05-24 |
| KR20080075105A (ko) | 2008-08-14 |
| JP2009516023A (ja) | 2009-04-16 |
| CN101305042A (zh) | 2008-11-12 |
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